CN103194086B - Synthetic method of aminopropionic acid-containing fluorescent brightener - Google Patents
Synthetic method of aminopropionic acid-containing fluorescent brightener Download PDFInfo
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- CN103194086B CN103194086B CN201310123045.3A CN201310123045A CN103194086B CN 103194086 B CN103194086 B CN 103194086B CN 201310123045 A CN201310123045 A CN 201310123045A CN 103194086 B CN103194086 B CN 103194086B
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Abstract
The invention discloses a synthetic method of an aminopropionic acid-containing fluorescent brightener. The existing method can be used for improving the reaction system of a DSD acid triazine fluorescent brightener to a certain extent, but fails in improving the productivity effectively. The synthetic method of the aminopropionic acid-containing fluorescent brightener is characterized in that triple condensation raw material organic amine 3-[(2-ethoxy)amino] propionic acid derivative is completely or partially salified with DSD acid to obtain a DSD acid organic ammonium salt aqueous solution; and then mono-condensation, double condensation and triple condensation reactions are orderly performed to obtain the aminopropionic acid-containing fluorescent brightener. The reaction time of the synthetic method provided by the invention is equivalent to that of the existing preparation method; in the reaction state that the concentration of the final product brightener is 10-12%, the viscosity of the mono-condensation reaction material system is only about one tenth of that of the material system with the concentration of final product brighter of 7-8% in the existing process; and therefore, the utilization rate of the reaction equipment is improved and the production cost is reduced as much as possible.
Description
Technical field
The present invention relates to white dyes field, specifically a kind of synthetic method containing alanine derivatives white dyes.
Background technology
Along with growth in the living standard, people are further strong to the requirement of color.Because white dyes has brightening, increases the effect of gorgeous and blast, meet the visual requirement of people.DSD acid triazines white dyes has obtained application widely in industries such as weaving, washing composition and paper, and its common synthetic method is: first, at the low temperature of 0-10 ℃, pH value is below 3, cyanuric chloride and DSD acid-respons; Then,, at 20-40 ℃, under pH value 3-7, carry out two contractings with aromatic amine and react; Finally, then with organic amine under reflux conditions, pH value 8-10 carries out three contractings reactions and obtains product.The synthetic route of above-mentioned reaction is as follows:
Through the development of last 100 years, the production technique of DSD acid triazines white dyes is very ripe.But the material thickness problem of a contracting reaction fails to solve well all the time in disulfonic acid series whitening agent preparation process.In whitening agent preparation process, a contracting reaction later stage, reaction mass is a kind of thickness state of intimate colloidal, has seriously affected normally carrying out of reaction.In order to guarantee the quality of product, the product concentration of reacting final only has 7-8%, produces a large amount of trade effluents, plant factor wretched insufficiency.
For some, the aromatic amine of containing water-soluble group is not as the whitening agent of the synthetic disulfonic acid series such as aniline, Ortho Toluidine, para-totuidine, and the water-soluble extreme difference of a contracting reaction product, has seriously affected normally carrying out of two contracting reactions.
All the time, people attempt to solve the material thickness problem in disulfonic acid series whitening agent preparation process by various means.
Japanese Patent JP47039216 etc. propose zinc oxide, magnesium oxide as acid binding agent, add nonionogenic tenside to carry out a contracting reaction.In JP48058024 mono-contracting reaction, add nonionogenic tenside and organic or inorganic an alkali metal salt as sodium-chlor, sodium sulfate, sodium-acetate etc.In the one contracting reaction such as JP49005128, add urea and nonionogenic tenside Scourol400, in two contracting reactions, add acetic acid.Poland Patent PL188490 proposes to carry out two contracting reactions with ammonium salt or the triethanolamine salt of DSD acid, introduces DSD acid ammonium salt in reaction.
Above-mentioned these methods are all by additionally adding the irrelevant compound of some and product and auxiliary agent to regulate the state of reaction system in reaction process.Adding of tensio-active agent causes mother liquor foaming, and increase the COD of waste water, increase aftertreatment difficulty, salt add the load that has increased aftertreatment desalination, not only increase product cost and also greatly increased burden prepared by product liquid formulation, the COD and the total nitrogen that have increased waste liquid, cause last handling process complexity, runs counter to the management philosophy of modern environmental protection anuria.
In Poland Patent PL164830, aniline carries out a contracting with cyanuric chloride and reacts in propyl alcohol-frozen water solution.One contracting reaction of English Patent GB1355218, Japanese Patent JP48073579 cyanuric chloride, DSD acid is carried out in acetone-frozen water solution.Aniline and cyanuric chloride reaction product 2-amino-4 in Czech patents CS162583,6-dichlorotriazine is carried out two contractings and is reacted in ethanolic soln with DSD acid disodium salt.Aforesaid method is in condensation reaction, to introduce organic solvent.Organic solvent add the viscosity problem that has solved reaction process, improved the quality of product.But maximum shortcoming is exactly the introducing of reaction solvent, has increased widely the production cost of product; In addition, inevitably there is processing and the pollution problem of organic solvent in the introducing of organic solvent.
All these measures have all improved the reaction system of DSD acid triazines white dyes to a certain extent above, but fail effectively to enhance productivity.Based on considering of the each side such as reaction cost, people carry out expanded reproduction, still can only implement by the simple conversion unit that expands.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect that above-mentioned prior art exists, a kind of synthetic method containing alanine derivatives white dyes is provided, the characteristic that it utilizes organic ammonium salt not react with cyanuric chloride in the situation that pH value is lower, by the dual control of temperature of reaction and pH value, one contracting, two contracting reactions are all carried out under the state of DSD acid organic ammonium salt, to solve the material thickness problem of reaction system.
For this reason, the technical solution used in the present invention is as follows: a kind of synthetic method containing alanine derivatives white dyes, it is characterized in that: by three contracting reaction raw materials organic amine 3-[(2-hydroxyethyls) amino] all or part of salify of propanoic derivatives and DSD acid, obtain the DSD acid organic ammonium salt aqueous solution;
Under the condition that be 1.5-3 at 0-15 ℃, pH value by the described DSD acid organic ammonium salt aqueous solution, be slowly added dropwise in the frozen water solution of cyanuric chloride and carry out a contracting reaction, keep temperature of reaction, use 15-20% aqueous sodium hydroxide solution adjusting pH value; React in the generation liquid obtaining and add aniline to carry out two contracting reactions in a contracting, temperature of reaction is controlled at 15-40 ℃, at 3-7, in a contracting and two contracting reactions, organic amine is existed by 15-20% aqueous sodium hydroxide solution adjusting pH value with the state of salify; Two contracting reactions are complete, and with highly basic, out pH value is controlled at 8-10, under reflux conditions carries out three contracting reactions by free organic amine, obtains containing alanine derivatives white dyes, and its structural formula is:
Described organic amine 3-[(2-hydroxyethyl) amino] structural formula of propanoic derivatives is as follows:
NH(C
2H
4OH)C
2H
4COR
In above-mentioned two structural formulas, R=-NH
2or-OR1, wherein: R
1=H or C
1-C
4alkyl.
The present invention utilizes organic ammonium salt in the situation that pH value is lower, the characteristic not reacting with cyanuric chloride, by the dual control of temperature of reaction and pH value, a contracting, two contracting reactions are all carried out under the state of DSD acid organic ammonium salt, solve the material thickness problem of reaction system.
Reaction equation of the present invention is as follows:
As preferably, described organic amine 3-[(2-hydroxyethyl) amino] propanoic derivatives for the consumption of DSD acid salify be the 10-100% of three contracting reaction theory consumptions, more preferably 15-25%, 45-55% or 90-100%; Carrying out before three contracting reactions, add organic amine 3-[(2-hydroxyethyl) amino] propanoic derivatives, make the total amount of organic amine reach the 105-120% of three contracting reaction theory consumptions, make to participate in the excessive 5-20% of organic amine that three contractings are reacted, three contractings are fully reacted.
As preferably, in a contracting reaction, temperature of reaction is 5-8 ℃, and pH value is 1.5-2.5; In two contracting reactions, temperature of reaction is 18-25 ℃, and pH value is 3.5-5.5; In three contracting reactions, temperature of reaction is 90-105 ℃, and pH value is 8-9.
Under optimum condition, prepare white dyes, product purity can reach 93%, meets or exceeds the Product Level of common technique.
In the present invention, in one contracting reaction, organic amine adds, can greatly reduce the viscosity of the first step condensation reaction material, whole material system has good mobility under stirring, the viscosity of reaction mass with add the amount of organic amine and the concentration of material to have direct relation.In specific scope, make the viscosity of reaction system lower with the organic amine consumption of DSD acid salify, such as the 15-25% that salify organic amine consumption is theoretical consumption, 45-55%, when 90-100%, the viscosity of reaction system only becomes 1/10th of salt system for not adding organic amine, even less.Within the scope of certain material concentration, the viscosity of reaction system is relatively little.In the present invention, when product concentration is that 10-12% material viscosity is lower, 1/10th while being about former handicraft product concentration 7-8%, concentration increases or reduces within the specific limits, and material viscosity all increases to some extent.
When two contracting pH value in reaction are when higher, easily dissociate out with the organic amine of DSD acid salify, easily there is competing reaction, cause product purity to decline.Therefore, when the acid-soluble solution of DSD, preferably add part organic amine, after two contractings have been reacted, required organic amine amount is reacted in polishing three contractings again.
In the present invention,, after two contractings are reacted, dissociate out with the organic amine of DSD acid salify, continue to participate in three contracting reactions, do not increase the overall consumption of organic amine in whitening agent preparation process.
Compared with existing preparation method, the present invention does not add any compound or the auxiliary agent except reactant in reaction process; Reduce in existing preparation method desalination burden in the last handling process that adds generation of extra salt; Solve the foaming problem causing due to the tensio-active agent additionally adding; Reduce the COD of waste liquid, and waste liquid total amount; Get rid of in a contracting reaction and introduced cost increase and the pollution problem that organic solvent produces.
Reaction times of the present invention is suitable with existing preparation method, under the response behaviour of finished product whitening agent concentration 10-12%, the viscosity of one contracting reaction mass system is only 1/10th left and right of the material system viscosity of existing technique finished product whitening agent concentration 7-8%, greatly improve the utilization ratio of conversion unit, made production cost be able to the decline of maximum possible.
Embodiment
Further illustrate the present invention below in conjunction with embodiment, but do not limit the present invention.
Embodiment 1:
3-[(2-hydroxyethyl by the DSD acid of 0.015mol with 0.03mol) amino] methyl propionate is mixed with the solution about 30g, for subsequent use.
In 250ml four-hole bottle, the cyanuric chloride of 0.0305mol is suspended in the frozen water of 115g, under stirring, slowly drips DSD acid 3-[(2-hydroxyethyl) amino] methyl propionate solution, keep pH value=2-3.With 15% sodium hydroxide solution adjust pH 2-2.5 left and right, be incubated 6-8 ℃ of reaction, about 3-5hr, detects amino with amino reagent and disappears, and a contracting has been reacted.
Reaction mass is warming up to 18 ℃, adds the aniline of about 0.295mol, drips 15% sodium hydroxide solution, keeps pH value 4-5.5, and temperature of reaction 20-25 ℃ is complete to two contracting reactions.
Keep temperature of reaction, the about 0.5hr of sodium hydroxide solution that slowly drips 0.3mol in reaction solution dropwises, the about 10-11 of pH value.To the 3-[(2-hydroxyethyl of adding 0.003mol in reaction solution) amino] methyl propionate, be warming up to backflow.Sodium hydroxide solution with 15% keeps pH value 8-10, and about 2-4hr reaction is complete, the about 8.5-9g of consumption sodium hydroxide.
Sampling analysis: fluorescent brightener levels 88%.
Embodiment 2:
3-[(2-hydroxyethyl by the DSD acid of 0.015mol with 0.003mol) amino] propionic acid amide and 0.012mol sodium hydroxide solution be mixed with the solution about 30g, for subsequent use.
In 250ml four-hole bottle, the cyanuric chloride of 0.0305mol is suspended in the frozen water of 115g, under stirring, slowly drips DSD acid 3-[(2-hydroxyethyl) amino] propionic acid amide solution, keep pH value=2-3.
With 15% sodium hydroxide solution adjust pH 2-2.5 left and right, be incubated 6-8 ℃ of reaction.About 3-5hr, detects amino with amino reagent and disappears, and a contracting has been reacted.
Reaction mass is warming up to 18 ℃, adds the aniline of about 0.295mol, drips 15% sodium hydroxide solution, keeps pH value 4-5.5, and temperature of reaction 20-25 ℃ is complete to two contracting reactions.
Keep temperature of reaction, the about 0.5hr of sodium hydroxide solution that slowly drips 0.03mol in reaction solution dropwises, the about 9-10 of pH value.To the 3-[(2-hydroxyethyl of adding 0.03mol in reaction solution) amino] propionic acid amide, be warming up to backflow.Sodium hydroxide solution with 15% keeps pH value 8-10, and about 2-4hr reaction is complete, the about 8.5-9g of consumption sodium hydroxide.
Sampling analysis: fluorescent brightener levels 93%.
Claims (5)
1. the synthetic method containing alanine derivatives white dyes, it is characterized in that: by three contracting reaction raw materials organic amine 3-[(2-hydroxyethyls) amino] all or part of salify of propanoic derivatives and DSD acid, obtain the DSD acid organic ammonium salt aqueous solution;
Under the condition that be 1.5-3 at 0-15 ℃, pH value by the described DSD acid organic ammonium salt aqueous solution, be slowly added dropwise in the frozen water solution of cyanuric chloride and carry out a contracting reaction, keep temperature of reaction, use 15-20% aqueous sodium hydroxide solution adjusting pH value; React in the generation liquid obtaining and add aniline to carry out two contracting reactions in a contracting, temperature of reaction is controlled at 15-40 ℃, at 3-7, in a contracting and two contracting reactions, organic amine is existed by 15-20% aqueous sodium hydroxide solution adjusting pH value with the state of salify; Two contracting reactions are complete, and with highly basic, out pH value is controlled at 8-10, under reflux conditions carries out three contracting reactions by free organic amine, obtains containing alanine derivatives white dyes, and its structural formula is:
Described organic amine 3-[(2-hydroxyethyl) amino] structural formula of propanoic derivatives is as follows:
NH(C
2H
4OH)C
2H
4COR
In above-mentioned two structural formulas, R=-NH
2or-OR
1, wherein: R
1=H or C
1-C
4alkyl;
Described organic amine 3-[(2-hydroxyethyl) amino] propanoic derivatives for the consumption of DSD acid salify be the 10-100% of three contracting reaction theory consumptions, carrying out before three contracting reactions, add organic amine 3-[(2-hydroxyethyl) amino] propanoic derivatives, make the total amount of organic amine reach the 105-120% of three contracting reaction theory consumptions.
2. the synthetic method containing alanine derivatives white dyes according to claim 1, it is characterized in that described organic amine 3-[(2-hydroxyethyl) amino] propanoic derivatives for the consumption of DSD acid salify be 15-25%, 45-55% or the 90-100% of three contracting reaction theory consumptions.
3. the synthetic method containing alanine derivatives white dyes according to claim 1, is characterized in that, in a contracting reaction, temperature of reaction is 5-8 ℃, and pH value is 1.5-2.5.
4. the synthetic method containing alanine derivatives white dyes according to claim 1, is characterized in that, in two contracting reactions, temperature of reaction is 18-25 ℃, and pH value is 3.5-5.5.
5. the synthetic method containing alanine derivatives white dyes according to claim 1, is characterized in that, in three contracting reactions, temperature of reaction is 90-105 ℃, and pH value is 8-9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1243276A (en) * | 1968-08-06 | 1971-08-18 | Sandoz Ltd | Novel triazinyl stilbene derivatives |
| US4386965A (en) * | 1980-07-03 | 1983-06-07 | Ciba-Geigy Corporation | Process for obtaining coating compositions of improved whiteness |
| JPS60134096A (en) * | 1983-12-17 | 1985-07-17 | 日本曹達株式会社 | Production of coated paper |
| DE3502038A1 (en) * | 1985-01-23 | 1986-07-24 | Sandoz-Patent-GmbH, 7850 Lörrach | AQUEOUS BRIGHTENING DEVICES AND THEIR USE IN THE PAPER LINE |
| US5266078A (en) * | 1990-07-03 | 1993-11-30 | W. R. Grace & Co.-Conn. | Enhancement of fluorescent whitening agents: water-soluble phosphonates and carboxylates for coating paper |
| EP1300514A1 (en) * | 2001-10-05 | 2003-04-09 | Bayer Aktiengesellschaft | Use of aqueous brightening compositions to brighten natural and synthetic materials |
-
2013
- 2013-03-14 CN CN201310123045.3A patent/CN103194086B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1243276A (en) * | 1968-08-06 | 1971-08-18 | Sandoz Ltd | Novel triazinyl stilbene derivatives |
| US4386965A (en) * | 1980-07-03 | 1983-06-07 | Ciba-Geigy Corporation | Process for obtaining coating compositions of improved whiteness |
| JPS60134096A (en) * | 1983-12-17 | 1985-07-17 | 日本曹達株式会社 | Production of coated paper |
| DE3502038A1 (en) * | 1985-01-23 | 1986-07-24 | Sandoz-Patent-GmbH, 7850 Lörrach | AQUEOUS BRIGHTENING DEVICES AND THEIR USE IN THE PAPER LINE |
| US5266078A (en) * | 1990-07-03 | 1993-11-30 | W. R. Grace & Co.-Conn. | Enhancement of fluorescent whitening agents: water-soluble phosphonates and carboxylates for coating paper |
| EP1300514A1 (en) * | 2001-10-05 | 2003-04-09 | Bayer Aktiengesellschaft | Use of aqueous brightening compositions to brighten natural and synthetic materials |
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